ABSTRACT
We have employed (2 + 1) resonance enhanced multiphoton ionization spectroscopy to investigate the 3d and 4s Rydberg states of the NO molecule when bound to the surface of Rg(x) clusters (Rg = rare gas). We observe that the spectra of the NO-Ar(x) species converge in appearance as x increases, and this is discussed in terms of two Rg atoms interacting with the NO+ core, with other Rg atoms being "outside" the Rydberg orbital. We show that the interaction of each of the Rg atoms with the NO is essentially independent for the NO-Rg2 complexes: both by comparing our spectra for Rydberg states of NO-Rg and NO-Rg2, and from the results of ab initio calculations on NO+ - Rg and NO+ - Rg2. In addition, we discuss the disappearance of some electronic bands upon complexation in terms of Franck-Condon factors that are very sensitive to the angular coordinate. We relate our results to those of the bulk by comparing to the previously reported electronic spectroscopy of NO in both Rg matrices and He nanodroplets.
ABSTRACT
We have employed (2+1) resonance-enhanced multiphoton ionization spectroscopy to record electronic absorption spectra of NO-Rg (Rg=Ne,Ar,Kr) van der Waals complexes. The nitric oxide molecule is the chromophore, and the excitation corresponds to an electron being promoted from the 2ppi* orbital to 3dsigma, 3dpi, and 3ddelta Rydberg states. We review the ordering of the 3dlambda states of NO and use this as a basis for discussing the 3d components in the NO-Rg complexes, in terms of the interactions between the Rydberg electron, the core, and the Rg atom. Predissociation of the H' 2Pi state occurs through the F2Delta state for NO-Ar and NO-Kr, and this will be considered. We shall also outline problems encountered when trying to record similar spectra for NO-Xe, related to the presence of atomic Xe resonances.
